CN107987680B - Water-based epoxy graphene anticorrosive paint - Google Patents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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Abstract
The invention relates to the field of anticorrosive coatings, and particularly relates to a preparation method of a two-component water-based epoxy graphene anticorrosive coating. The invention uses epoxy polyether addition product to emulsify epoxy resin to prepare epoxy resin emulsion, and uses amino polyether and polyamine to react with epoxy resin to prepare polyether modified epoxy amine addition product curing agent. Preparing zinc powder slurry as a component A from the epoxy resin amine adduct, zinc powder, pigment and filler and graphene; the silicate sol is prepared by jointly hydrolyzing a silane coupling agent and silicate, and the silicate sol is mixed with the epoxy resin emulsion to be used as a component B. The modification of the appropriate amount of graphene to the zinc powder slurry and the modification of the silicate sol to the epoxy emulsion obviously improves the corrosion resistance of the water-based zinc-rich primer, achieves the same corrosion resistance effect, and can greatly reduce the using amount of zinc powder. The obtained water-based primer has low VOC content, greatly reduces the pollution of organic solvent and zinc powder to the environment, and eliminates fire and potential safety hazard. The paint has good storage stability, safe and convenient construction, fast drying of the coating, strong adhesive force of the paint film and excellent corrosion resistance.
Description
Technical Field
The invention relates to the field of water-based anticorrosive coatings, in particular to a preparation method of an environment-friendly two-component water-based epoxy graphene zinc-rich anticorrosive coating.
Background
The zinc-rich coating protects the steel substrate from corrosion by virtue of the electrochemical protection effect of the zinc powder, and has an excellent anticorrosion effect. The method is widely applied to ship manufacturing, container manufacturing, ocean engineering, petrochemical engineering storage tanks, steel structures and bridge corrosion prevention. The traditional zinc-rich primer mainly comprises three types of solvent type epoxy zinc-rich primer, alcohol-soluble inorganic zinc silicate primer and water-based inorganic zinc-rich paint. The former two are solvent-based paints, and the epoxy zinc-rich primer is largely used in container manufacturing and bridge corrosion prevention. The alcohol-soluble inorganic zinc-rich primer is widely applied to steel plate precoating in shipbuilding and container manufacturing industries. Because of containing a large amount of organic solvent and large zinc powder content, zinc fog is generated during welding, and the use of the zinc fog is increasingly limited along with increasingly strict domestic environmental protection requirements. The water-based inorganic zinc-rich primer does not contain VOC, has excellent solvent resistance, and is widely applied to the corrosion prevention of the inner wall of an oil tank. But the flexibility is poor, and the requirement on substrate rust removal is also high. The primer is not suitable for being used as a pre-coating primer or a zinc-rich primer in occasions with high requirements on flexibility, such as container manufacturing, railway vehicle manufacturing and the like. Waterborne epoxy zinc rich primers are the best choice in these applications. For 2016, container coatings were waterborne on a large scale. The primer for internal use, external use and steel structure is mostly water-based epoxy zinc-rich primer. Compared with solvent-based epoxy zinc-rich primer, the water-based epoxy zinc-rich primer has certain difference in corrosion resistance under the same zinc powder content due to the fact that the resin is relatively hydrophilic, and is easy to foam, and red rust is generated at the scratch part early. The zinc powder content is therefore generally between 70 and 80% by weight of the dry film. During welding, zinc fog is generated due to volatilization of the zinc powder, and the physical health of workshop personnel is greatly damaged. Reducing the zinc powder content results in a rapid decrease in the corrosion resistance of the primer.
In recent years, the addition of graphene has a good effect on improving the corrosion resistance of the primer with lower zinc content. Graphene is a new material with a single-layer sheet structure composed of carbon atoms. Is a two-dimensional material with the thickness of only one carbon atom, and has excellent conductivity and larger sheet-to-diameter ratio. Can be applied to anticorrosive paint by utilizing the conductivity or the sealing performance. Chinese patent 201510497999.X discloses a two-component graphene anticorrosive coating. Wherein the component A comprises the following components in percentage by weight: 0.1-5% of graphene; 0-35% of zinc powder; 30-70 wt% of filler; 10-20 wt% of epoxy resin with solid content of 54%; 10-20 wt% of solvent. According to the invention, the graphene is added into the anticorrosive coating, so that the anticorrosive effect is improved, the content of zinc powder is greatly reduced, the zinc mist generated during welding is greatly reduced, and the environment-friendly effect is achieved. Chinese patent 201410725574.5 discloses a graphene modified epoxy zinc-rich primer and a preparation method thereof. Wherein the weight parts of the components are as follows: 15-30 parts of modified epoxy resin, 0.3-5 parts of graphene, 2-8 parts of butanol, 4-10 parts of toluene, 0.3-3 parts of anti-settling agent and 70-90 parts of zinc powder. Has good antirust, heat-resistant, oil-resistant, water-resistant and solvent-resistant performances and excellent adhesive force. Chinese patent 201410841675.9 discloses a water-based graphene composite coating, which is composed of water-based resin, graphene, aniline oligomer derivatives, water and an auxiliary agent, wherein the mass percentage of the graphene is 0.01-4%, and the graphene and the aniline oligomer derivatives form pi-pi bonds to be uniformly dispersed in the water-based resin. The prepared water-based graphene composite coating has large binding force with a metal substrate and low emission of organic volatile matters, and the composite coating has good water permeability and salt mist resistance and strong protective capability, and can be used as a heavy-duty anticorrosive coating to be applied to relatively severe corrosive environments such as ships and bridges. The graphene is used as a two-dimensional structure material with a sheet diameter ratio being extremely large, and can obtain a strong sealing effect under the condition of a small using amount, so that the anti-corrosion performance of the coating is improved. However, since graphene has a large specific surface area, it is difficult to wet and disperse in an aqueous solution, and if good dispersion in a coating material cannot be achieved, the effect of graphene is difficult to exert regardless of whether it is based on conduction or shielding. And due to the low surface energy characteristic of graphene, the graphene is easy to concentrate on the surface, so that the adhesion of the coating is reduced.
In addition, in the primer, due to good conductivity of graphene, when a paint film has defects, the graphene, the metal substrate and the electrolyte form a corrosion battery, so that the corrosion risk is accelerated.
Disclosure of Invention
The invention takes inorganic modified epoxy emulsion as a base material, and prepares the water-based epoxy graphene anticorrosive paint by matching with zinc powder, graphene, a dispersing agent, an epoxy curing agent, pigment and filler and the like.
Preparing graphene slurry by using graphene, a dispersing agent and a self-made epoxy curing agent, and grinding the graphene slurry together with zinc powder, the epoxy curing agent, pigment and filler to obtain graphene zinc powder slurry (component A);
and (2) preparing a silane prepolymer by hydrolyzing and polymerizing a siloxane monomer, continuously hydrolyzing the silane prepolymer to obtain silicate sol, and mixing the silicate sol and the epoxy emulsion to obtain the inorganic modified epoxy emulsion (component B).
A. And B, mixing the two components before construction. The water-based epoxy zinc-rich primer is modified by adding silicate sol and graphene, so that the corrosion resistance is obviously improved, and the content of zinc powder is reduced by half compared with that of the conventional epoxy zinc-rich primer. During construction, the paint can be diluted by tap water, has no burning and explosion hazard, and reduces VOC emission by more than 70% compared with solvent-based paint.
1 preparation of graphene zinc slurry (component A)
The graphene zinc slurry formulation is shown in the following table.
| Name of raw material | Parts by weight |
| Graphene | 4-6 |
| Dispersing agent | 5-10 |
| Epoxy curing agent | 50-80 |
| Solvent(s) | 40-80 |
| Zinc powder | 350-500 |
| Barium sulfate | 30-70 |
| Superfine heavy calcium carbonate | 30-70 |
| Aluminium triphosphate | 20-50 |
| Zinc phosphate | 20-50 |
| Composite phosphate | 20-50 |
| Organic bentonite | 5-15 |
| Fumed silica | 3-5 |
Wherein the graphene is reduced graphene, the carbon content of the graphene is more than or equal to 99 percent, the oxygen content of the graphene is less than or equal to 0.1 percent, the particle size of the graphene is 2-10 mu m, and the number of layers is less than or equal to 7. The solvent may be alcohols, ether alcohols, aromatic hydrocarbons and mixtures thereof. The zinc powder is 500-800 mesh zinc powder.
The dispersant may be Haimines 'D-983, FN211, W19, EFKA 4560, OMG's 0451. The barium sulfate is industrial top grade precipitated barium sulfate or modified barium sulfate.
The zinc phosphate is superfine zinc phosphate with fineness of more than 600 meshes, the aluminium triphosphate is silicon dioxide modified aluminium triphosphate such as APW-II of Guangxi chemical research institute, and the composite phosphate is strontium calcium phosphate, such as SW-111 and CW-291 of Halox. The organic bentonite may be Bentoni SD-2, Bengel 818, 828, 858 of Hamming. The fumed silica may be a non-treated or a hydrophobically treated fumed silica, such as the winning A-200, A-380, R106.
The epoxy curing agent is a polyether modified epoxy amine adduct. The preparation formula comprises:
wherein the epoxy resin is bisphenol A type liquid epoxy resin, such as E51 or E44 epoxy resin. The polyetheramines are low molecular weight amino-terminated polyethylene glycols, for example D230, D403, ED-600, ED 900.
The preparation process comprises the following steps: adding epoxy resin, propylene glycol methyl ether and diethyl ether into a flask, stirring and dissolving to obtain epoxy resin liquid for later use;
adding isophorone diamine and polyether amine into a four-neck flask, introducing nitrogen, heating to 50 ℃, gradually adding epoxy resin liquid, controlling the temperature to be not higher than 70 ℃, completing the addition for about 1 hour, and continuing to keep the temperature of 65-70 ℃ and stirring for reaction for 1 hour after the addition is completed. Obtaining the epoxy curing agent.
The preparation process of the graphene zinc slurry comprises the following steps:
adding an epoxy curing agent, a solvent and a dispersing agent into a stirring container, uniformly stirring, adding graphene, and dispersing at a high speed for 30 minutes; adding zinc powder, barium sulfate, superfine calcium bicarbonate, zinc phosphate, aluminum tripolyphosphate and composite phosphate, and stirring at high speed for 30 minutes. Adding organic bentonite and gas-phase silicon dioxide, and stirring at high speed for 15 minutes. Filtering with 100-mesh stainless steel net. And obtaining the graphene zinc powder slurry.
The zinc powder slurry is naturally placed for 1 month, and the slurry layering, gas production and zinc powder bottom sinking conditions are observed.
Preparation of inorganic modified epoxy emulsion (component B):
the inorganic modified epoxy emulsion is prepared by mixing silicate ester sol and epoxy emulsion.
Preparation of epoxy emulsion: epoxy resin, polyether emulsifier and polyisocyanate are reacted to prepare epoxy polyether addition compound. Then the addition product is taken as an emulsifier to be mixed with epoxy resin and cosolvent, and the mixture is stirred and emulsified to prepare epoxy resin emulsion.
The epoxy emulsion preparation formula comprises:
the epoxy resin can be E-51, E-44, E-20 epoxy resin or their mixture, wherein E-51 is 618 of Lanxingxing new material, SM618 of Sanmu, EPON-828 of Hexion, Yueyang petrochemical CYD-128, E-44 epoxy resin is 6101 of Lanxining new material, Yueyang petrochemical CYD-144, E-20 epoxy resin is 601 of Lanxining new material, and Yueyang petrochemical CYD-011.
The polyether emulsifier can be fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether. Such as polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether or mixtures thereof, for example, as emulsifiers OP-10, OP-15, OP-20, TX-10, TX-15, TX-21 from the chemical plant Hainan, Jiangsu province. It may also be an EO/PO block polyether, such as the L35, F-38, L45 polyethers from the Hainan chemical plant, PE6400, PE6800, PE10500 from BASF. The cosolvent can be propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol butyl ether, high boiling point aromatic solvent S-100/S150 or a mixture thereof.
The polyisocyanate may be an aromatic diisocyanate such as TDI, an alicyclic diisocyanate such as isophorone diisocyanate IPDI, an aliphatic diisocyanate such as HDI. The softened water is deionized water, and can be prepared by reverse osmosis method or ion exchange method, and its conductivity is less than or equal to 20 μ s/cm.
The preparation process comprises the following steps:
adding diisocyanate into a four-neck flask, heating to 65-70 ℃, adding fatty alcohol (or alkylphenol) polyoxyethylene ether and EO/PO block polyether while stirring, continuing to stir and keep the temperature for 2-3h, adding part (10-20%) of epoxy resin, heating to 80-90 ℃, and continuing to keep the temperature and stir for 2-3 h. Adding the rest (80-90%) of epoxy resin, stirring uniformly, gradually adding water, and stirring until phase inversion to form O/W type epoxy emulsion. Pouring into a beaker, and emulsifying for 30 minutes by using a high-shear emulsifying machine to obtain the epoxy emulsion.
Preparation of silicate sol: partial hydrolysis of silicate monomer and silane coupling agent to obtain silane prepolymer. The prepolymer is further hydrolyzed to obtain silicate sol.
First, a silane prepolymer was prepared, the formulation being as follows:
the silane coupling agent can be glycidoxypropyl trimethoxy siloxane, glycidoxypropyl triethoxy siloxane, methacryloxypropyl triethoxy siloxane, vinyl triethoxy silane, vinyl trimethoxy silane, vinyl tri (β -methoxyethoxy) silane, etc. the ion exchange resin is a strongly acidic ion exchange resin, such as Dow's IR100NA, Brandt's C100E, Shanghai Kaiping resin D001 resin, water is deionized water, and the conductivity is less than or equal to 20 mus/cm.
The preparation process comprises the following steps:
silicate ester monomer, silane coupling agent, ethanol and ion exchange resin are added into the four-mouth flask. Stirring at low speed for 5 minutes; dropwise adding water while stirring, continuously stirring for 1-1.5 hours after the dropwise adding is finished within 1-1.5 hours, and standing overnight. Obtaining the silane prepolymer.
Then, the prepolymer is taken as the basis to be continuously hydrolyzed to prepare silicate sol, and the formula is as follows:
wherein the surfactant is fatty alcohol polyether or alkylphenol polyether, the cosolvent is propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol butyl ether, and the ion exchange resin is strong acid ion exchange resin, such as Dow's IR100NA, Britain's C100E, and Shanghai Kaiping resin D001 resin. The water is deionized water, and the conductivity is less than or equal to 20 mu s/cm.
The preparation process comprises the following steps: adding water, cosolvent, surfactant, ion exchange resin, and silane prepolymer into a container with stirring at a speed adjustable, and stirring for 2-6 hr until the mixed solution is transparent solution or uniform semitransparent microemulsion to obtain silicate sol.
The sol was then mixed with an epoxy emulsion according to the formulation given in the table below.
Inorganic modified epoxy emulsion formula
| Serial number | Name of raw materials | Parts by mass |
| 1 | Water (W) | 5-15 |
| 2 | Cellulose, process for producing the same, and process for producing the same | 0.2-1.0 |
| 3 | Preservative | 0.1-0.5 |
| 4 | Silicate sol | 15-25 |
| 5 | Epoxy emulsion | 60-80 |
| 6 | Defoaming agent | 0.05-0.3 |
Wherein the cellulose is a medium molecular weight hydroxyethylcellulose such as sublong's 250HBR, NP330, Aksu's EBS 451, Luzhou's North D30000.
Adding water and a preservative into a stirring container, adding cellulose while stirring, continuing to stir for 1 hour after the addition, then adding silicate sol, epoxy emulsion and a defoaming agent, and stirring for 1 hour. Obtaining the inorganic modified epoxy emulsion. Coating construction and performance detection:
the two components are proportioned: component A and component B are 2.5-3:1 (weight ratio)
Gradually adding the component A into the component B under stirring, uniformly stirring, adding 5-15% (by weight) of water for dilution, and applying. Workability and coating film appearance test: after mixing the two components, adding 10% of water for dilution, brushing the mixture by using a wool brush, or adding 5% of water for dilution, and spraying the mixture by using a high-pressure airless sprayer. And (4) inspecting the phenomena of construction smoothness, wet film sagging, leveling, bubbles, dry film color, brush marks, orange peel, pinholes, cracks and the like. The general performance is that 1 channel is coated on a 7 multiplied by 150 multiplied by 0.25 tinplate, and the thickness is 20 to 30 mu m; the salt spray test sample is brushed for 2 times, and the thickness is 40-60 mu m. Drying the appearance of the coating film for 15 minutes at normal temperature, and drying the coating film for 30 minutes at 50-70 ℃; other property tests of the paint film were carried out after 7 days of drying at 23. + -. 2 ℃.
The invention prepares zinc powder slurry by epoxy resin amine addition product, zinc powder, filler and graphene, and prepares graphene modified water-based epoxy zinc-rich primer by matching with inorganic modified epoxy resin emulsion modified by silicate sol. The modification of the epoxy emulsion by adding the zinc powder slurry and the silicate sol into the graphene obviously improves the corrosion resistance of the water-based zinc-rich primer. The invention can replace solvent-based zinc-rich primer, water-based epoxy zinc-rich primer with high zinc powder content and water-based inorganic zinc-rich primer, and can be used as pre-coating primer and zinc-rich primer for coating of container production lines; or used as shop primer for shipbuilding and railway vehicle production, or used as heavy anti-corrosive paint for anti-corrosive coating of bridges and steel structures.
Detailed Description
1. Preparation of graphene zinc powder slurry (component A)
Epoxy curing agents were prepared and the example formulations are shown in table 1.
TABLE 1 preparation examples of epoxy curing agents
The preparation process comprises the following steps: adding E51 epoxy resin, propylene glycol methyl ether and propylene glycol ethyl ether into a 2000ml flask, stirring and dissolving to obtain epoxy resin liquid; adding isophorone diamine and ED-600 polyether amine into a four-neck flask, introducing nitrogen, heating to 50 ℃, gradually adding epoxy resin liquid, controlling the temperature to be 65-70 ℃, completing the addition for about 1 hour, and continuing to keep the temperature of 65-70 ℃ and stirring for reaction for 1 hour after the addition is completed. Obtaining the epoxy curing agent.
As can be seen from Table 1, epoxy curing agents with good state can be obtained when the equivalent ratio of active hydrogen to epoxy is 3.6-5: 1.
Graphene zinc slurries were prepared with the formulations shown in table 2.
TABLE 2 graphene zinc slurry formulation
The preparation process comprises the following steps: adding an epoxy curing agent, S-150/propylene glycol butyl ether, sec-butyl alcohol and a D-983 dispersing agent (Hamming) into a stirring container, and stirring at a low speed for 5 minutes; adding zinc powder, precipitated barium sulfate, 1250-mesh superfine heavy calcium carbonate, 600-mesh superfine zinc phosphate (Guangxi chemical research institute), AZP-II aluminum tripolyphosphate (Guangxi chemical research institute), SW-111 composite phosphate (HALOX) and graphene, and stirring at high speed for 30 minutes. Adding organic bentonite and gas-phase silicon dioxide, and stirring at high speed for 15 minutes. Filtering with a 100-mesh stainless steel net to obtain the graphene zinc powder slurry.
2. Preparation of inorganic modified epoxy emulsion (component B)
Examples of epoxy emulsion synthesis are shown in Table 3.
TABLE 3 examples of epoxy emulsion Synthesis
The preparation process comprises the following steps: adding TDI into a four-neck flask, heating to 65-70 ℃, adding fatty alcohol (or alkylphenol) polyoxyethylene ether and EO/PO block polyether while stirring, continuing stirring and keeping the temperature for 2-3h, adding a first batch of epoxy resin, heating to 80-90 ℃, and continuing keeping the temperature and stirring for 2-3 h. Adding the rest epoxy resin, stirring uniformly, gradually adding water, and stirring until phase inversion to form O/W type emulsion. Pouring into a beaker, and emulsifying for 30 minutes by using a high-shear emulsifying machine to obtain the epoxy emulsion.
Preparation of silicate sol:
the silane prepolymer preparation formulation is shown in table 4.
TABLE 4 silane prepolymer formulations
Preparation process of silane prepolymer
Silicate ester monomer, silane coupling agent, ethanol and ion exchange resin are added into the four-mouth flask. Stirring at low speed for 5 minutes; dropwise adding water during stirring, continuously stirring for 1.5 hours after dropwise adding within 1.5 hours, and standing overnight. Filtering with a 120-mesh net to obtain the silane prepolymer.
Silicate sols were then prepared based on this prepolymer, and the formulation is given in Table 5.
TABLE 5 silicate Sol formulation
The preparation process comprises the following steps: adding deionized water, cosolvent, surfactant, ion exchange resin and silane prepolymer into a container with speed-regulating stirring, stirring for 5h, and filtering with 120-mesh screen to obtain silicate sol.
The silicate sol was mixed with the epoxy emulsion according to the formulation in table 6.
TABLE 6 inorganic modified epoxy emulsion formulations
The preparation process comprises the following steps: adding water and a preservative into a stirring container, adding cellulose while stirring, continuing to stir for 1 hour after the addition, then adding silicate sol, epoxy emulsion and a defoaming agent, and stirring for 1 hour. Filtering with 120-mesh net to obtain the inorganic modified epoxy emulsion.
3. Preparing the water-based zinc-rich primer, constructing and detecting the performance.
The formulation ratios of the aqueous zinc-rich examples 31-36 are shown in Table 7. The coating properties are shown in Table 8.
TABLE 7 waterborne Zinc-rich primer formulation
TABLE 8 waterborne epoxy anticorrosion primer Performance
The comparative formulation is shown in Table 9. The coating properties are shown in Table 10.
TABLE 9 common waterborne epoxy Zinc-rich primer formulation
| Name of raw materials | Comparative example 1 | Comparative example 2 |
| Component A | ||
| W-18 dispersant | 5 | 5 |
| Epoxy curing agent 8538 | 50 | 50 |
| S-100 | 30 | 30 |
| Sec-butyl alcohol | 25 | 25 |
| 500 mesh zinc powder | 625 | 400 |
| Precipitated barium sulfate | 125 | |
| 1250 mesh superfine heavy calcium carbonate | 100 | |
| SW-111 composite phosphate | 20 | 20 |
| SD-2 organic bentonite | 10 | 8 |
| AS-200 fumed silica | 3.5 | 4 |
| B component | ||
| Water (W) | 19.2 | 19.2 |
| NP330 cellulose | 0.4 | 0.4 |
| Preservative | 0.3 | 0.3 |
| Epoxy emulsion 6520 | 220 | 220 |
| Dipropylene glycol methyl ether | 15 | 15 |
| Defoaming agent | 0.1 | 0.1 |
The formulations of comparative examples 1 and 2 had no graphene component for component a and no silicate sol for component B. Wherein the epoxy emulsion and curing agent are from Hansen, and the remaining raw material sources are the same as in the previous examples.
The preparation process comprises the following steps:
the component A comprises: adding epoxy curing agent, solvent and dispersant into a stirring container, stirring uniformly, adding zinc powder, barium sulfate, superfine heavy calcium and composite phosphate, and stirring at high speed for 30 minutes. Adding organic bentonite and gas-phase silicon dioxide, and stirring at high speed for 15 minutes. Filtering with 100 mesh net to obtain component A.
And B component:
adding water and a preservative into a stirring container, adding cellulose while stirring, continuing stirring for 1 hour after the addition is finished, then adding the epoxy emulsion and the defoaming agent, and stirring for 30 minutes. Filtering with 120 mesh net to obtain component B.
Table 10 coating performance of the invention compared to the comparative example.
| Item | Example 31 | Comparative example 1 | Comparative example 2 |
| Solids content | 71.2 | 79.3 | 79.3 |
| Zinc content (finished state)% | 38.1 | 61.1 | 39.1 |
| Zinc content (dry film)% | 53.5 | 78.8 | 50.5 |
| Paint film appearance | Is even and flat | Is even and flat | Is even and flat |
| Workability | Is normal | Is normal | Is normal |
| Sag resistance, mum | 150 | 150 | 150 |
| Surface drying time, min | 15 | 15 | 15 |
| Adhesion force, grade | 1 | 1 | 1 |
| Flexibility, mm | 2 | 2 | 2 |
| Impact strength, cm | 50 | 50 | 50 |
| Salt spray test, h | 720h has no change | Foaming for 300h | Rust in 300h |
| VOC，g/L | 8.9 | 8.9 | 8.9 |
In comparative example 1, the content of dry film zinc powder reaches 78.8 percent, and the foaming phenomenon is generated after the salt spray test is carried out for 300 hours; comparative example 2 the dry zinc powder content was similar to that of example 31, but tarnishing occurred after 300h of the salt spray test.
Claims (8)
1. The water-based epoxy graphene anticorrosive paint is characterized by comprising a component A, namely graphene zinc powder slurry, and a component B, namely inorganic modified epoxy emulsion; the A component graphene zinc slurry comprises the following components:
the component B comprises inorganic modified epoxy emulsion:
according to the weight ratio of the component A to the component B being 2.5-3:1,
the silicate sol formula in the component B comprises the following components:
silane prepolymer formulation:
2. the water-based epoxy graphene anticorrosive paint according to claim 1, wherein the epoxy curing agent in the component A is synthesized according to a formula:
3. the water-based epoxy graphene anticorrosive paint according to claim 1, wherein the formula of the epoxy emulsion in the component B is as follows:
4. the water-based epoxy graphene anticorrosive paint according to claim 2, characterized in that the preparation process of the epoxy curing agent comprises the following steps: adding epoxy resin, propylene glycol methyl ether and propylene glycol ethyl ether into a flask, stirring and dissolving to obtain epoxy resin liquid for later use; adding isophorone diamine and polyether amine into a four-neck flask, introducing nitrogen, heating to 50 ℃, gradually adding epoxy resin liquid, controlling the temperature to be not higher than 70 ℃, finishing the addition for 1h, and then continuing to keep the temperature of 65-70 ℃ and stirring for reaction for 1h to obtain the epoxy curing agent.
5. The water-based epoxy graphene anticorrosive paint as claimed in claim 1, wherein the preparation process of graphene zinc slurry comprises the following steps: adding an epoxy curing agent, a solvent and a dispersing agent into a stirring container, uniformly stirring, adding graphene, and dispersing at a high speed for 30 minutes; adding zinc powder, barium sulfate, superfine calcium bicarbonate, zinc phosphate, aluminum tripolyphosphate and composite phosphate, stirring at high speed for 30 minutes, adding organic bentonite and fumed silica, stirring at high speed for 15 minutes, and filtering with 100-mesh stainless steel net. And obtaining the graphene zinc powder slurry.
6. The water-based epoxy graphene anticorrosive paint according to claim 1, characterized in that the preparation process of the epoxy emulsion comprises the following steps: adding diisocyanate into a four-neck flask, heating to 65-70 ℃, adding alkylphenol polyoxyethylene ether and EO/PO block polyether while stirring, continuing to stir and preserve heat for 2-3h, adding 10-20% of epoxy resin, heating to 80-90 ℃, continuing to preserve heat and stir for 2-3h, adding the rest epoxy resin, stirring uniformly, gradually adding water and stirring until phase inversion to form O/W type epoxy emulsion, pouring into a beaker, and emulsifying for 30 min by using a high-shear emulsifying machine to obtain the epoxy emulsion.
7. The water-based epoxy graphene anticorrosive paint according to claim 1, characterized in that a silane prepolymer preparation process comprises the following steps: adding silicate ester monomer, silane coupling agent, ethanol and ion exchange resin into the four-mouth flask, and stirring at low speed for 5 minutes; and dripping water during stirring, continuously stirring for 1-1.5 hours after the dripping is finished within 1-1.5 hours, and standing overnight to obtain the silane prepolymer.
8. The water-based epoxy graphene anticorrosive paint according to claim 1, characterized in that a silicate sol preparation process comprises the following steps: adding water, cosolvent, surfactant, ion exchange resin, and silane prepolymer into a container with stirring at a speed adjustable, and stirring for 2-6 hr until the mixed solution is transparent solution or uniform semitransparent microemulsion to obtain silicate sol.
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